Metal compound of omicron-hydroxyazo dyestuffs



Patented Aug. 22, 1933 METAL COMPOUND F o-nYnnoxYAzo DYESTUFFS Hans 'Krzikalla, Mannheim, and'Franz Blucmmel, Seckenhcim, Germany, assignors to General Aniline Works, Inc., NewYork, N. Y., a Corporation of Delaware No Drawing. Application November 20 1928, Serial No. 320,747, and in Germany November 6 Claims. (01; 260-12 7 Our present invention relates to new complex metal compounds or 'o-hydroxyazo dyestuffs, more particularly it relates to complex metal compounds obtainable by treating the o-hydroxy- 6 azo dyestuffs, prepared from a diazo compound of o-aminophenol or a substitution product thereof containing, for instance, one or more chlorine atoms, or one or more nitro groups, or both or I these substituents and m-phenylenediamine or 10 its nitro, halogen or' alkyl substitution products, with compounds of metals capable of forming complex metal compounds with the said dyestufis. The treatment may be carried out for instance by boiling or heating the said dyestuffs with the Iii-metal compounds at ordinary or elevated pressure. Especially the resulting complexchromium or copper compounds are suitable for dyeing leather and the resulting dyeings are very fast I to light.

The following examples will further illustrate how the said invention may be carried out into practical effect but the invention is not limited to these examples. The parts are by weight,

Example 1 38.5 parts of the o-hydroxyazo dyestufl? obtainable from diazotized 4-nitro-2-aminopheno1-6- sulphonic acid and p-chlor-m-phenylenediamine are heated at 105 centigrade for 2 hours in an autoclave with a solution containing 9.1 parts of chromium oxid (CraOa) and 14 parts of 85 per cent formic acid in 600 parts of water. The dyestufl. obtained on salting out gives brown dyeings on leather which are very test to light.

The copper compound of the same o-hydroxyazo dyestufl, which can be easily obtained by boiling the latter with copper acetate or copper sulphate, gives similar dyeings on leather.

. v Slightly more reddish brown shades on leather 46 are obtained with the similarly prepared chromium compound of the dyestuff containing p-nitro-m-phenylenediamine instead of p-chlorm-phenylenediamine.

Example 2 About 36 parts of the azo dyestufi obtainable formate and about 4 parts of 85 percent formic acid, the dyestufl being filtered by suction and dried. It gives 'fast yellow brown dyeings on leather. The chromium compound of the same o-hydroxyazo dyestufl gives shades having amore reddish tinge.

Whatweclaimis:

1. As products, the complex compounds of a metal selected from the group consisting of copper and chromium with o-hydroxyazo dyestuffs .of the general formula N: Y Y

wherein one X stands for chlorine or the nitro group, one X for hydrogen or the sulfonicacid group and the other X's represent hydrogen or chlorine or the nitro group, and wherein one Y in ortho-position to one of the amino groups represents the linkage to theazo group, one Y stands for hydrogen or for a substituent of the group consisting of halogen, thealkyl radicle and the nitro group, and the other Ys represent hydrogcn.

2. As products, the complex compounds of a metal selected from the group consisting of coppeer and chromium with o-hydroxyazo dyestufls oi thegeneral formula 011 NH: I

, ,x N= Y i Y x x y NH:

wherein one X stands for chlorine or the nitro I group, one X stands for the sulfonic acid group and the other X's represent hydrogen, chlorine or the nitro group and wherein one Y in orthoposition to one of the amino groups represents the linkage to the azo group, one Y-stands for hydrogen or for a substituent of the group consisting of halogen, the alkyl radicle and the nitro group, and the other Y's represent hydrogen.

3. As products, the complex compounds of a 2 i metalselected from the per and chromium with o-hydroxyazodyestufls of the general formula I bl IHz wherein one X stands for chlorine or the nitro group and the other Xs representhydrogen or chlorine or the nitro group and wherein one Y in ortho position to one of the-aminogroups represents the linkage to the azogroup, one Y stands for hydrogen or the methyl Y stands for hydrogen and Z represents y o chlorine or the nitro group. I

v 4. As products, the complex compounds of a 7 metal selected from the group consisting of copper and chromium with o-hydroxyazo dyestuffs of the general formula i OH s H0 I N=Ns I v V I NH:

group consisting of copgroup and the other I I in-whichthe azo group giving brown shades on leather.

5. As products, the complex compounds of a 7 metal selected from the group per and chromium with the consisting of copo-hydroxyazo dyestufl corresponding to the general formula: V

HOaS

in which the azo group is connected to an ortho position to one of the amino groups in the phenylene diamine nucleus, the said compounds giving brown shades on leather.

. 6. As a product, the complex chromium compound of the o-hydroxyazo dyestufi correspondingto the formula:

is connected to an ortho position to one of the amino; groups in thephenylene diamine nucleus, the said compounds HANSKRZIKAJ FRANZ BLUEMMEL, 

